Merging Borylation and Desaturation to Access Arylboronates from Carbonyls

We present a NaHMDS-promoted method for the efficient and highly selective synthesis of aryl boronates from carbonyl compounds. This approach offers several advantages, including environmental sustainability, the absence of halogenated waste, and no need for catalysts and additives. These protocols enable the late-stage borylation of biorelevant compounds, thus offering a versatile platform for synthesizing diverse naphthalene derivatives from carbonyls. Experimental studies suggest that the reaction involves alkenyl C-O bond borylation and desaturation processes. Notably, the NaHMDS/diboron reagent system demonstrates unprecedented oxidative properties rather than its more commonly encountered reductive properties, which will open new avenues for designing transformations using this platform.